CN110684159A - Preparation method of dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer - Google Patents
Preparation method of dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer Download PDFInfo
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Abstract
The invention relates to the field of food science, and discloses a preparation method of a dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer, aiming at the problems of irregular polymer shape, few effective binding sites and low mass transfer speed in the traditional macromolecular imprinted technology in the prior art, which comprises the following four preparation steps: (1) activated magnetic Fe3O4Nanoparticles to produce alkylated magnetic Fe3O4A nanoparticle; (2) synthesizing magnetic nanocrystalline cellulose; (3) grafting a dendrimer; (4) the magnetic nano-crystalline cellulose surface imprinted polymer modified by the dendrimer is prepared. The invention combines the nanometer material and the surface imprinting technology, can effectively realize the regular tree-shaped high molecular structure, the obtained surface imprinted polymer has larger specific surface area, higher adsorption rate, stronger adsorption capacity and hole capacity, the molecular surface can provide rich imprinted sites, the imprinted polymer can realize the rapid separation, and the imprinting efficiency is improved.
Description
Technical Field
The invention relates to the field of food science, in particular to a preparation method of a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer.
Background
The molecular imprinting technology is a technology for preparing a high molecular polymer with specific recognition performance on target molecules, and surface molecular imprinting is one of the key research points in the technical field of molecular imprinting at present. The surface molecular imprinting method is a method for forming an imprinted polymer by a polymer which is newly raised on the basis of an original preparation method of a molecular imprinting technology, overcomes the defects that the particle size of the polymer prepared in the original method is not uniform enough, and the imprinted molecules are embedded too deeply and are not easy to elute, and effectively reduces the embedding by utilizing the surface imprinting method and is easy to elute the imprinted molecules.
The patent number CN2013107390846, the patent name of which is 'a preparation method of magnetic zinc ion surface imprinted polymer', firstly synthesizes magnetic Fe by utilizing a 'coprecipitation method' and a 'sol-gel method'3O4@SiO2Microspheres, and treated with an acid to increase their surface hydroxyl content; the polymerizable double bond is then introduced into the Fe by means of a "two-step process3O4@SiO2The surface of the microsphere is grafted with amino groups by using an aminosilane coupling agent and then acid anhydrideAnd an amino group to form a double bond; finally using Fe3O4@SiO2Taking microspheres as a carrier, Zn (II) as a template, ethylene glycol dimethacrylate as a cross-linking agent, methacrylic acid and salicylaldoxime as monomers to carry out polymerization reaction, and washing off the template Zn (II) after the reaction is finished to obtain Fe3O4@SiO2The surface of the microsphere is provided with a polymer layer with a large amount of Zn (II) imprinted cavities.
The defects of the surface imprinted polymer are that the shape is irregular, the effective binding sites are few, the adsorption capacity is limited and the mass transfer speed is slow.
Disclosure of Invention
The invention provides a preparation method of a magnetic nanocrystalline cellulose surface imprinted polymer modified by a tree-like macromolecule, aiming at overcoming the problems of irregular polymer shape, few effective binding sites, low mass transfer speed and the like in the traditional macromolecule imprinting technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 35-45 deg.C, and adding magnetic Fe3O4Nano particles, stirring and reacting at constant temperature, magnetically separating, drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, and stirring for dissolving to obtain a mixed solution; magnetic Fe to alkylate3O4Adding the nanoparticles into the mixed solution, heating to 45-50 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at constant temperature, and performing magnetic separation to obtain the magnetic materialNanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules, the dendrimer magnetic nanocrystalline cellulose and acetonitrile, adding the functional monomer, the initiator and the cross-linking agent, uniformly mixing, magnetically stirring for reaction at 40-50 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product.
The alkylation may be with magnetic Fe3O4Nanoparticles are modified in Fe3O4The surface activity of the nano particles is increased by introducing small molecules, unsaturated alkyl and the like on the surfaces of the nano particles, so that the magnetic Fe3O4The nano particles have better biocompatibility and dispersibility, small particle size, easy attachment and distribution and can be quickly and effectively bonded with biological molecules.
The nano-crystalline cellulose is cheap and easy to obtain, has good hydrophilicity, high mechanical strength, biocompatibility and modifiability, is non-toxic and harmless, has large specific surface area and strong adsorption capacity, and is an excellent carrier for surface imprinted molecules.
The dendritic polymer polyamidoamine is introduced, a large divergent dendritic molecular chain is arranged on the dendritic polymer polyamidoamine, the surface functional groups of the dendritic polymer can form a composite material through stable metal ions such as molecular chain ion interaction, acid-base interaction and the like, and can also realize multifunctional modification through covalent bond grafting, and the internal cavity can be loaded with target molecules in a wrapping mode, and the target molecules can be used as host molecules and can be effectively and selectively combined with object molecules.
Preferably, the isothermal reaction time in step (2) is 35-50 min.
Preferably, the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine in the step (3) is 1: 5-9.
Preferably, the functional monomer in step (4) is acrylamide.
Acrylamide is active in chemical property and easy to generate polymerization reaction to form polyacrylamide, so that the dendritic macromolecules are driven to generate crosslinking reaction to form a three-dimensional ordered surface imprinted polymer material with a stable structure, and powerful guarantee is provided for forming holes with fixed shapes inside.
Preferably, in the step (4), the template molecule is at least one of dimethyl phthalate or dimethyl phthalate.
Dimethyl phthalate and dimethyl phthalate are plasticizers which have strong dissolving power with various resins, have higher thermal stability, can be dissolved with various resins, have good film forming property, adhesiveness and water resistance, and can be used as template molecules because the demolding is easy.
Preferably, the mass ratio of the template molecules to the functional monomers in the step (4) is 1: 4-8.
The functional monomer is a monomer providing a specific functional group, and the function is that the functional monomer can interact with the imprinting molecule and is in a proper position with the cross-linking agent molecule, so that the imprinting molecule is finally provided with a desired orientation and positioning, and the template molecule only provides a template function for the formation of the hole, so that the two are required to be limited in a proper ratio range.
Preferably, the initiator in step (4) is dibenzoyl peroxide.
Dibenzoyl peroxide is a strong oxidizing agent, flammable, and chemically unstable, and is used herein as a chemical crosslinking initiator.
Preferably, the crosslinking agent in step (4) is ethylene dimethacrylate.
Preferably, the isothermal reaction time in step (1) is 30-40 min.
Therefore, the invention has the following beneficial effects:
(1) mixing nanocrystalline cellulose and magnetic Fe by coprecipitation method3O4Combining with nanometer particle to obtain magnetic nanocrystalline cellulose with controllable particle diameter, grafting dendrimer with acryloyl group modified on the magnetic nanocrystalline celluloseThe amide amine solution is prepared into a tree-shaped polymer structure which is regular, a large number of holes are formed in the amide amine solution, and the holes can keep the shape of the amide amine solution stable, so that the amide amine solution has high selectivity when being combined with guest molecules again;
(2) the nano material is combined with the dendrimer polyamidoamine solution, so that the specific surface area is large, a large number of unique chemical structures of amino exist on the surface, rich imprinting sites can be provided, the imprinted polymer has a good adsorption effect, and the adsorption capacity of the imprinted polymer is increased;
(3) with magnetic Fe3O4When the surface imprinted polymer material of the nanoparticles is separated, the rapid separation can be realized only by a simple external magnetic field under the condition of non-covalent bond combination or weak covalent bond combination, and the imprinting efficiency is high.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a preparation method of a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 40 deg.C, and adding magnetic Fe3O4Stirring and reacting for 35min at constant temperature, magnetically separating, and drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, stirring and dissolving to obtain a mixed solution, wherein the mass ratio of the nanocrystalline cellulose to the itaconic acid is 1: 5; magnetic Fe to alkylate3O4Adding nanoparticles into the mixed solution, heating to 48 deg.C, adding initiatorCarrying out constant temperature reaction for 43min by using diisopropyl peroxydicarbonate, and carrying out magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine is 1:7, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules of dimethyl phthalate, dendritic magnetic nanocrystalline cellulose and acetonitrile, adding a functional monomer of acrylamide, an initiator of dibenzoyl peroxide and a cross-linking agent of ethylene dimethacrylate, uniformly mixing, magnetically stirring for reaction at 45 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product, wherein the mass ratio of the template molecules to the functional monomer is 1: 6.
Example 2
The difference from the embodiment 1 is that the preparation method of the dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 35 deg.C, and adding magnetic Fe3O4Stirring and reacting for 30-40min at constant temperature, magnetically separating, and drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, stirring and dissolving to obtain a mixed solution, wherein the mass ratio of the nanocrystalline cellulose to the itaconic acid is 1: 4; magnetic Fe to alkylate3O4Adding the nano particles into the mixed solution, heating to 45 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at a constant temperature for 35min, and performing magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine is 1:5, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules of dimethyl phthalate, dendritic magnetic nanocrystalline cellulose and acetonitrile, adding a functional monomer of acrylamide, an initiator of dibenzoyl peroxide and a cross-linking agent of ethylene dimethacrylate, uniformly mixing, magnetically stirring for reaction at 40 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product, wherein the mass ratio of the template molecules to the functional monomer is 1: 4.
Example 3
The difference from the embodiment 1 is that the preparation method of the dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 45 deg.C, and adding magnetic Fe3O4Stirring and reacting for 40min at constant temperature, magnetically separating, and drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, stirring and dissolving to obtain a mixed solution, wherein the mass ratio of the nanocrystalline cellulose to the itaconic acid is 1: 6; magnetic Fe to alkylate3O4Adding the nano particles into the mixed solution, heating to 50 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at a constant temperature for 50min, and performing magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine is 1:9, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules of dimethyl phthalate, dendritic magnetic nanocrystalline cellulose and acetonitrile, adding a functional monomer of acrylamide, an initiator of dibenzoyl peroxide and a cross-linking agent of ethylene dimethacrylate, uniformly mixing, magnetically stirring for reaction at 50 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product, wherein the mass ratio of the template molecules to the functional monomer is 1: 8.
Example 4
The difference from the embodiment 1 is that the preparation method of the dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 38 deg.C, and adding magnetic Fe3O4Stirring and reacting for 33min at constant temperature, magnetically separating, and drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, stirring and dissolving to obtain a mixed solution, wherein the mass ratio of the nanocrystalline cellulose to the itaconic acid is 1: 6; magnetic Fe to alkylate3O4Adding the nano particles into the mixed solution, heating to 50 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at a constant temperature for 50min, and performing magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine is 1:6, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules of dimethyl phthalate, dendritic magnetic nanocrystalline cellulose and acetonitrile, adding a functional monomer of acrylamide, an initiator of dibenzoyl peroxide and a cross-linking agent of ethylene dimethacrylate, uniformly mixing, magnetically stirring for reaction at 50 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product, wherein the mass ratio of the template molecules to the functional monomer is 1: 5.
Example 5
The difference from the embodiment 1 is that the preparation method of the dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer comprises the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 43 deg.C, and adding magnetic Fe3O4Stirring and reacting for 38min at constant temperature, magnetically separating, and drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthesizing magnetic nanocrystalline cellulose: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, stirring and dissolving to obtain a mixed solution, wherein the mass ratio of the nanocrystalline cellulose to the itaconic acid is 1: 4; magnetic Fe to alkylate3O4Adding the nano particles into the mixed solution, heating to 49 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at a constant temperature for 47min, and performing magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine is 1:8, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules of dimethyl phthalate, dendritic magnetic nanocrystalline cellulose and acetonitrile, adding a functional monomer of acrylamide, an initiator of dibenzoyl peroxide and a cross-linking agent of ethylene dimethacrylate, uniformly mixing, magnetically stirring for reaction at 46 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product, wherein the mass ratio of the template molecules to the functional monomer is 1: 7.
Conclusion analysis: the specific surface area represents the surface adsorption capacity of the surface imprinted polymer material, the larger the specific surface area is, the larger the adsorption capacity is, the pore volume represents the accommodation capacity of the surface imprinted polymer to guest molecules, and the larger the value is, the better the performance of the surface imprinted polymer material is.
The embodiments described above are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the claims below.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer is characterized by comprising the following specific preparation steps:
(1) activated magnetic Fe3O4Nano-particles: adding 3-propyl trimethoxy silane into deionized water, heating to 35-45 deg.C, and adding magnetic Fe3O4Nano particles, stirring and reacting at constant temperature, magnetically separating, drying to obtain alkylated magnetic Fe3O4A nanoparticle;
(2) synthetic magnetic nanocrystalline fibersVitamin C, vitamin C: adding nanocrystalline cellulose and itaconic acid into an aqueous solution of acetic acid, and stirring for dissolving to obtain a mixed solution; magnetic Fe to alkylate3O4Adding the nano particles into the mixed solution, heating to 45-50 ℃, adding an initiator diisopropyl peroxydicarbonate, reacting at constant temperature, and performing magnetic separation to obtain magnetic nanocrystalline cellulose;
(3) grafting a dendrimer: adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding magnetic nanocrystalline cellulose into the dendrimer polyamidoamine solution, adding a condensing agent dicyclohexylcarbodiimide, performing magnetic separation, and drying to obtain dendrimer magnetic nanocrystalline cellulose;
(4) preparing a dendrimer modified magnetic nanocrystalline cellulose surface imprinted polymer: mixing template molecules, the dendrimer magnetic nanocrystalline cellulose and acetonitrile, adding the functional monomer, the initiator and the cross-linking agent, uniformly mixing, magnetically stirring for reaction at 40-50 ℃, extracting by using ether to remove the template molecules, and separating to obtain a finished product.
2. The preparation method of the dendrimer-modified magnetic nano-crystalline cellulose surface imprinted polymer according to claim 1, wherein the mass ratio of the nano-crystalline cellulose to the itaconic acid in the step (2) is 1: 4-6.
3. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the isothermal reaction time in step (2) is 35-50 min.
4. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the mass ratio of the magnetic nanocrystalline cellulose to the dendrimer polyamidoamine in the step (3) is 1: 5-9.
5. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the functional monomer in step (4) is acrylamide.
6. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the template molecule in step (4) is at least one of dimethyl phthalate or dimethyl phthalate.
7. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the mass ratio of the template molecules to the functional monomers in step (4) is 1: 4-8.
8. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the initiator in step (4) is dibenzoyl peroxide.
9. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the crosslinking agent in step (4) is ethylene dimethacrylate.
10. The method for preparing the dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer according to claim 1, wherein the isothermal reaction time in step (1) is 30-40 min.
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| CN111514867A (en) * | 2020-06-03 | 2020-08-11 | 李娟� | Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof |
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| US20080064810A1 (en) * | 2004-09-10 | 2008-03-13 | Borje Sellergren | Imprinting Using Dendrimers as Templates |
| CN107141406A (en) * | 2017-05-26 | 2017-09-08 | 浙江海洋大学 | A kind of Magnetic Carboxylate nano-crystal cellulose amino functional molecular imprinted polymer on surface |
| CN107238643A (en) * | 2017-05-08 | 2017-10-10 | 常州大学 | The preparation of the silicon dioxide modified indium-tin oxide electrode of branching shape molecular engram |
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2019
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| US20080064810A1 (en) * | 2004-09-10 | 2008-03-13 | Borje Sellergren | Imprinting Using Dendrimers as Templates |
| CN107238643A (en) * | 2017-05-08 | 2017-10-10 | 常州大学 | The preparation of the silicon dioxide modified indium-tin oxide electrode of branching shape molecular engram |
| CN107141406A (en) * | 2017-05-26 | 2017-09-08 | 浙江海洋大学 | A kind of Magnetic Carboxylate nano-crystal cellulose amino functional molecular imprinted polymer on surface |
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| HAO, YI等: "Selective extraction of gallic acid in pomegranate rind using surface imprinting polymers over magnetic carbon nanotubes", 《ANALYTICAL AND BIOANALYTICAL CHEMISTRY》 * |
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| CN111514867A (en) * | 2020-06-03 | 2020-08-11 | 李娟� | Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof |
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